CN112537775B - Method for preparing ZSM-22 molecular sieve - Google Patents
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- C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
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Abstract
The invention relates to a method for preparing a ZSM-22 molecular sieve, which comprises the step of carrying out crystallization treatment on a mixture formed by a silicon source, an aluminum source, an alkali source, a template agent, urea and water to obtain the molecular sieve. In the mixture, SiO is used2Silicon source calculated as Al2O3Calculated as Al source and OH‑The calculated molar composition of the alkali source, the urea, the template and the water is as follows: SiO 22/Al2O315 to 500; templating agent/SiO20.01 to 0.5; OH group‑/SiO20.01 to 0.50; h2O/SiO29 to 30; Urea/SiO20.005 to 0.50. The molecular sieve crystal prepared by the method has the advantages of sheet shape, small thickness and adjustable silicon-aluminum ratio, and meets different requirements for catalysts in chemical production.
Description
Technical Field
The invention belongs to the field of catalysts, and particularly relates to a method for preparing a ZSM-22 molecular sieve and the molecular sieve prepared by the method.
Background
The ZSM-22 molecular sieve is firstly synthesized by Dwyer et al of Mobil company in the 20 th century in 80 years, the main channel of the ZSM-22 molecular sieve is a one-dimensional elliptic straight channel, the opening of the channel is a 10-membered ring, the aperture is 0.46nm multiplied by 0.57nm, and the parameters of unit cells are
[Zeolites,1987,(7):393-397]。
Due to the mild acid property and the space shape-selective effect, the ZSM-22 molecular sieve is applied to the fields of isomerization reaction of straight-chain paraffin, olefin preparation from methanol, alkylation of aromatic hydrocarbon, hydrocracking, catalytic dewaxing, aromatization of paraffin and the like.
Both theoretical and experimental studies show that most of the reactions catalyzed by the ZSM-22 molecular sieve occur in the pore opening, so that the crystal morphology is an important factor influencing the catalytic performance of the molecular sieve.
The ZSM-22 molecular sieve is usually synthesized by a hydrothermal crystallization method, generally using organic templates such as 1,6 hexanediamine (US 4902406, US 5707600), ethylenediamine (US 4556477) and the like, uniformly mixing a silicon source, an aluminum source, an alkali source, the organic templates and water, crystallizing, and roasting to obtain the ZSM-22 molecular sieve. CN 105565339A (Shanxi institute of coal chemistry, China academy of sciences, USA, 2016.03.02) discloses a preparation method of a small-grain ZSM-22 molecular sieve, which comprises the steps of uniformly mixing one or more of 1-ethyl pyridine bromide, 1, 6-hexamethylene diamine, N-methyl imidazole biquaternary ammonium salt, diethylamine, N-butylamine and 1, 8-diaminooctane by using one or more of 1-ethyl pyridine bromide, 1, 6-hexamethylene diamine, N-methyl imidazole biquaternary ammonium salt, diethylamine, N-butylamine and 1, 8-diaminooctane as a template agent to form an initial gel mixture, adding one or more of active carbon, graphite, graphene, carbon black, starch microspheres, chitosan and polylactic acid microspheres, uniformly stirring, crystallizing, filtering and separating a solid product, washing the solid product to be neutral by using deionized water, drying and roasting to obtain the small-grain ZSM-22 molecular sieve. CN 107814392A (university of Henan university, 2017.10.12) discloses a preparation method of a ZSM-22 molecular sieve, which takes imidazole ionic liquid 1-ethyl-3 methyl-imidazole chloride ([ EMIm ] Cl) and 1-butyl-3 methyl-imidazole chloride ([ BMIm ] Cl) as structure directing agents and prepares the ZSM-22 molecular sieve by crystallization at 180 ℃. CN 109502607A (Shanxi institute of coal chemistry, China academy of sciences, USA, 2018.11.30) discloses a method for synthesizing a nano ZSM-22 molecular sieve, which comprises the steps of uniformly mixing a silicon source, an aluminum source, an alkali source, a template agent and deionized water to form an initial gel mixture, carrying out hydrothermal crystallization at 140-180 ℃ autogenous pressure to obtain a pre-crystallized solid, uniformly mixing the pre-crystallized solid, the alkali source, the template agent and the deionized water to form a mixture, carrying out hydrothermal crystallization at 140-180 ℃ autogenous pressure, washing, drying and roasting to obtain the nano ZSM-22 molecular sieve. The template agent is one or a mixture of more of 1-ethyl pyridine bromide, 1, 6-hexamethylene diamine, N-methyl imidazole biquaternary ammonium salt, diethylamine and 1, 8-diaminooctane. The ZSM-22 molecular sieve synthesized in the way is a rod-shaped or needle-shaped crystal, has small external specific surface area and large organic molecule diffusion resistance, cannot be used in chemical reaction with macromolecules, is easy to activate, and greatly limits the application of the ZSM-22 molecular sieve.
Chinese patent 201310047018.2 Zhejiang university 2013.02.01 discloses a method for synthesizing ZSM-22 molecular sieve by using a seed crystal method, wherein aluminum sulfate is used as an aluminum source, and tetraethoxysilane is used as a silicon source. Chinese patent CN201310353621.3 (institute of chemical and physical sciences, university of Chinese academy of sciences, 2013.08.14) discloses a method for synthesizing a ZSM-22 molecular sieve, wherein the ZSM-22 molecular sieve is used as a seed crystal, and an organic template is not used, and the ZSM-22 molecular sieve and the Me-ZSM-22 molecular sieve are synthesized by hydrothermal reaction under alkaline conditions. Chinese patent 201510072221.4 Zhejiang university 2015.02.11 discloses a method for synthesizing a ZSM-22 molecular sieve without an organic template and a seed crystal, wherein aluminum sulfate is used as an aluminum source, an alkali source is potassium hydroxide or sodium hydroxide, and the silicon source is tetraethyl orthosilicate or white carbon black. Chinese patent 201510708781.4 (Beijing chemical university, 2015.10.27) discloses a method for rapidly preparing a ZSM-22 molecular sieve by using seed crystals. However, the ZSM-22 molecular sieves synthesized by the method are all rod-shaped crystals.
Chinese patent 201510084713.5[ Heilongjiang university, 2015.02.16] discloses a preparation method of a ZSM-22 molecular sieve nanosheet: 1) preparing a prefabricated seed crystal by using aluminum sulfate octadecahydrate, ethyl orthosilicate, 1, 6-hexanediamine, potassium hydroxide and deionized water; 2) preparing gel by using aluminum sulfate octadecahydrate, silica sol, potassium hydroxide and deionized water; 3) crystallizing and roasting. The alkaline source used in the method is KOH, the prepared ZSM-22 molecular sieve nanosheets are stacked together, the first nanosheet is covered by the second nanosheet, the area of the first nanosheet is large, the exposed area of the first nanosheet is small, and the thickness of the first nanosheet reaches 20 nanometers. No diffusion advantage is exhibited compared to conventional ZSM-22 molecular sieves in rod or needle form.
CN 107285332A (Shanghai Petroleum chemical research institute, 2016.04.12, China petrochemical Co., Ltd.) discloses a synthesis method of a ZSM-22 molecular sieve and the ZSM-22 molecular sieve synthesized by the same, but a ZSM-22 molecular sieve nanosheet (Cryst Eng Comm,2016,18,5611) can be obtained only when the feeding silica-alumina ratio is high (about 200).
As can be seen from the above review, although the method for synthesizing the ZSM-22 molecular sieve is mature, it is difficult to synthesize ZSM-22 molecular sieve nanosheets, and the synthesis phase region thereof is narrow, thereby resulting in a great limitation in the application of ZSM-22 molecular sieves.
Disclosure of Invention
The technical problem to be solved by the invention is to provide a method for preparing a ZSM-22 molecular sieve aiming at the defects of the prior art, and the molecular sieve crystal prepared by the method has a flaky shape, is smaller in thickness and adjustable in silica-alumina ratio, and meets different requirements of chemical production on catalysts.
According to one aspect of the invention, a method for preparing a ZSM-22 molecular sieve is provided, which comprises the step of carrying out crystallization treatment on a mixture formed by a silicon source, an aluminum source, an alkali source, a template agent, urea and water to obtain the molecular sieve.
In some embodiments, the mixture is SiO2Calculated silicon source, calculated as Al2O3Calculated as Al source and OH-The calculated molar composition of the alkali source, the urea, the template and the water is as follows: SiO 22/Al2O315 to 500; templating agent/SiO20.01 to 0.5; OH group-/SiO20.01 to 0.50; h2O/SiO29 to 30; Urea/SiO20.005 to 0.50.
In some embodiments, the mixture is in SiO2Calculated silicon source, calculated as Al2O3Calculated as Al source and OH-The calculated molar composition of the alkali source, the urea, the template and the water is as follows: SiO 22/Al2O320 to 400; templating agent/SiO20.05 to 0.5; OH group-/SiO20.05 to 0.40; h2O/SiO210 to 26; Urea/SiO20.01 to 0.40.
In some embodiments, the mixture is in SiO2Calculated silicon source, calculated as Al2O3Calculated as Al source and OH-The molar composition of the alkali source, the urea, the template and the water is as follows: SiO 22/Al2O320 to 200; templating agent/SiO20.05 to 0.5; OH group-/SiO20.05 to 0.40; h2O/SiO210 to 26; Urea/SiO20.01 to 0.40.
In some embodiments, the mixture is SiO2Calculated silicon source, calculated as Al2O3Calculated as Al source and OH-The calculated molar composition of the alkali source, the urea, the template and the water is as follows: SiO 22/Al2O320 to 55; templating agent/SiO20.05 to 0.5; OH group-/SiO20.05 to 0.40; h2O/SiO210 to 26; Urea/SiO20.01 to 0.40.
In some embodiments, the silicon source comprises at least one of silica gel, silica sol, and tetraalkyl silicate, preferably silica sol.
In some embodiments, the aluminum source comprises at least one of sodium aluminate, aluminum nitrate, aluminum sulfate, aluminum oxide, aluminum hydroxide, and aluminum isopropoxide, preferably sodium aluminate.
In some embodiments, the templating agent is 1-ethylpyridinium bromide.
In some embodiments, the crystallization conditions comprise: the crystallization temperature is 80-180 ℃, and preferably 100-180 ℃; the crystallization time is 10 hours to 10 days, preferably 1 to 5 days.
According to another aspect of the present invention, there is provided a ZSM-22 molecular sieve prepared according to the above method, the molecular sieve crystals having a plate-like morphology with a crystal thickness of 8-20 nm.
In some embodiments, the molecular sieve has a silica to alumina ratio of 15 to 300.
Compared with the prior art, the method can be used for preparing SiO2/Al2O3Ratio is from low toThe ZSM-22 molecular sieve with the sheet shape is synthesized under high conditions, and the synthetic phase region is enlarged; the thickness of the crystal of the obtained molecular sieve is 8-20nm, which is beneficial to molecular diffusion and is not easy to accumulate carbon when used as a catalyst; the silica-alumina ratio of the obtained molecular sieve is 15-300, the limitation that the prior art can only synthesize the ZSM-22 molecular sieve with high silica-alumina ratio is broken through, the acid density of the molecular sieve can be adjusted according to the requirement, and the application range of the molecular sieve can be expanded.
Drawings
FIG. 1 is an SEM photograph of the molecular sieve prepared in example 1;
FIG. 2 is an SEM photograph of the molecular sieve prepared in example 2;
FIG. 3 is an SEM photograph of the molecular sieve prepared in comparative example 1;
fig. 4 is an SEM photograph of the molecular sieve prepared in comparative example 2.
Detailed Description
In order that the present invention may be more readily understood, the following detailed description of the invention is given by way of example only, and is not intended to limit the scope of the invention.
The operations and treatments involved in the present invention are conventional in the art unless otherwise specified.
The apparatus used in the present invention is an apparatus conventional in the art unless otherwise specified.
The raw materials involved in the specific embodiment of the invention are as follows:
(A) silica sol: containing SiO240 wt%, industrial product;
(B) sodium aluminate: containing Al2O3Amount 41 wt%, commercial product;
(C) 1-ethyl pyridine bromide: a commercially available product;
(D) urea, commercially available;
(E) sodium hydroxide: content 96 wt%, commercial product.
The detection method related in the specific embodiment of the invention is as follows:
(1) determination of the thickness of the molecular sieve:
and (3) importing the SEM picture of the prepared molecular sieve into Nano Measurer software, calibrating a ruler, and then carrying out software measurement on the thickness of the molecular sieve sheet, so as to obtain the thickness distribution of the sheet-shaped molecular sieve after ensuring that the statistics of the molecular sieve samples is more than or equal to 100, and measuring the average thickness of the molecular sieve.
(2) And (3) determining the silicon-aluminum ratio of the molecular sieve:
the composition of the molecular sieve is measured by adopting an ICP-AES internal standard method (analytical test technology and instrument, 2004,10(1), 30-33), and the silicon-aluminum ratio of the molecular sieve is obtained by calculating according to the measurement result of the content of Si and Al elements.
Example 1
Dissolving 3.72 g of 1-ethyl pyridine bromide, 0.06 g of sodium aluminate, 0.5 g of sodium hydroxide and 0.4 g of urea in 15.5 g of deionized water, slowly adding 10 g of silica sol under the condition of stirring, continuously stirring for one hour, then placing into a stainless steel reaction kettle with a polytetrafluoroethylene lining, and crystallizing for 4 days at 150 ℃. And after crystallization, filtering, washing and drying to obtain the ZSM-22 molecular sieve.
The material ratio (mol ratio) of the reactants is as follows: SiO 22/Al2O3180; 1-Ethyl pyridine bromide/SiO2＝0.3；OH-/SiO2＝0.2；H2O/SiO218; Urea/SiO2＝0.1。
The SEM photograph of the ZSM-22 molecular sieve prepared in example 1 is shown in FIG. 1, and the average thickness is about 10 nm, and the plate-shaped crystals are randomly staggered and are not regularly stacked. The silica-alumina ratio of the molecular sieve nano-sheet is 145.
Example 2
Except that the material ratio (mol ratio) of the reactants is as follows: SiO 22/Al2O3100; 1-Ethyl pyridine bromide/SiO2＝0.5；OH-/SiO2＝0.1；H2O/SiO 220; Urea/SiO2The procedure of example 1 was repeated except that 0.1 was used.
The SEM photograph of the prepared ZSM-22 molecular sieve is shown in figure 2, the average thickness is 10 nanometers, and the silica-alumina ratio is 101.
Example 3
Except that the material ratio (mol ratio) of the reactants is as follows: SiO 22/Al2O320; 1-Ethyl pyridine bromide/SiO2＝0.3；OH-/SiO2＝0.2；H2O/SiO218; Urea/SiO2The procedure of example 1 was repeated except that 0.1 was used.
The average thickness of the prepared ZSM-22 molecular sieve is 15 nanometers, and the silica-alumina ratio is 17.
Example 4
Except that the material ratio (mol ratio) of the reactants is as follows: SiO 22/Al2O3400; 1-Ethyl pyridine bromide/SiO2＝0.3；OH-/SiO2＝0.2；H2O/SiO218; Urea/SiO2The procedure of example 1 was repeated except that 0.1 was used.
The average thickness of the prepared ZSM-22 molecular sieve is 9 nanometers, and the silica-alumina ratio is 238.
Example 5
Except that the material ratio (mol ratio) of the reactants is as follows: SiO 22/Al2O3180; 1-Ethyl pyridine bromide/SiO2＝0.5；OH-/SiO2＝0.2；H2O/SiO218; Urea/SiO2The procedure of example 1 was repeated except that 0.1 was used.
The average thickness of the prepared ZSM-22 molecular sieve is 12 nanometers, and the silica-alumina ratio is 166.
Example 6
Except that the material ratio (mol ratio) of the reactants is as follows: SiO 22/Al2O3180; 1-Ethyl pyridine bromide/SiO2＝0.05；OH-/SiO2＝0.2；H2O/SiO218; Urea/SiO2The procedure of example 1 was repeated except that 0.1 was used.
The average thickness of the prepared ZSM-22 molecular sieve is 10 nanometers, and the silica-alumina ratio is 152.
Example 7
Except that the material ratio (mol ratio) of the reactants is as follows: SiO 22/Al2O3180; 1-Ethyl pyridine bromide/SiO2＝0.3；OH-/SiO2＝0.1；H2O/SiO218; Urea/SiO20.1 outerOtherwise, the same procedure as in example 1 was repeated.
The average thickness of the prepared ZSM-22 molecular sieve is 14 nanometers, and the silica-alumina ratio is 162.
Example 8
Except that the material ratio (mol ratio) of the reactants is as follows: SiO 22/Al2O3180; 1-Ethylpyridine bromide/SiO2＝0.3；OH-/SiO2＝0.5；H2O/SiO218; Urea/SiO2The procedure of example 1 was repeated except that 0.1 was used.
The average thickness of the prepared ZSM-22 molecular sieve is 8 nanometers, and the silica-alumina ratio is 96.
Example 9
Except that the material ratio (mol ratio) of the reactants is as follows: SiO 22/Al2O3180; 1-Ethyl pyridine bromide/SiO2＝0.3；OH-/SiO2＝0.05；H2O/SiO218; Urea/SiO2The procedure of example 1 was repeated except that 0.1 was used.
The average thickness of the prepared ZSM-22 molecular sieve is 14 nanometers, and the silica-alumina ratio is 169.
Example 10
Except that the material ratio (mol ratio) of the reactants is as follows: SiO 22/Al2O3180; 1-Ethyl pyridine bromide/SiO2＝0.3；OH-/SiO2＝0.2；H2O/SiO218; Urea/SiO2The procedure of example 1 was repeated except that 0.05 was used.
The average thickness of the prepared ZSM-22 molecular sieve is 14 nanometers, and the silica-alumina ratio is 146.
Example 11
Except that the material ratio (mol ratio) of the reactants is as follows: SiO 22/Al2O3180; 1-Ethyl pyridine bromide/SiO2＝0.3；OH-/SiO2＝0.2；H2O/SiO218; Urea/SiO2The procedure of example 1 was repeated except that 0.2 was used.
The average thickness of the prepared ZSM-22 molecular sieve is 12 nanometers, and the silica-alumina ratio is 156.
Example 12
Except that the material ratio (mol ratio) of the reactants is as follows: SiO 22/Al2O3180; 1-Ethyl pyridine bromide/SiO2＝0.3；OH-/SiO2＝0.2；H2O/SiO218; Urea/SiO2The procedure of example 1 was repeated except for 0.4.
The average thickness of the prepared ZSM-22 molecular sieve is 10 nanometers, and the silica-alumina ratio is 142.
Example 13
The same procedure as in example 1 was repeated, except that the crystallization temperature was 100 ℃.
The average thickness of the prepared ZSM-22 molecular sieve is 9 nanometers, and the silica-alumina ratio is 170.
Example 14
The same procedure as in example 1 was repeated, except that the crystallization temperature was 160 ℃.
The average thickness of the prepared ZSM-22 molecular sieve is 14 nanometers, and the silica-alumina ratio is 154.
Example 15
The same procedure as in example 1 was repeated, except that the crystallization temperature was 180 ℃.
The average thickness of the prepared ZSM-22 molecular sieve is 16 nanometers, and the silica-alumina ratio is 127.
Example 16
The same procedure as in example 1 was repeated, except that the crystallization time was 1 day.
The average thickness of the prepared ZSM-22 molecular sieve is 8 nanometers, and the silica-alumina ratio is 165.
Example 17
The same procedure as in example 1 was repeated, except that the crystallization time was 10 days.
The average thickness of the prepared ZSM-22 molecular sieve is 14 nanometers, and the silica-alumina ratio is 156.
Comparative example 1
Dissolving 19 g of 1-ethyl pyridine bromide, 2 g of sodium aluminate and 1.25 g of sodium hydroxide in 94 g of deionized water, slowly adding 60 g of silica sol under the condition of stirring, then adding 1.2 g of ZSM-22 molecular sieve seed crystal, continuously stirring for one hour, then placing into a stainless steel reaction kettle with a polytetrafluoroethylene lining, and dynamically crystallizing for 3 days at 150 ℃. And after crystallization, filtering, washing and drying to obtain 28.2 g of a solid product, wherein XRD detection results show that the solid product is a mixture of a low-crystallinity ZSM-22 molecular sieve and amorphous silicon-aluminum.
The material ratio (mol ratio) of the reactants is as follows: SiO 22/Al2O350; 1-Ethyl pyridine bromide/SiO2＝0.25；OH-/SiO2＝0.075；H2O/SiO2＝18。
The SEM photograph of the solid product obtained in comparative example 1 is shown in fig. 3, in which a large amount of amorphous silica-alumina is present and the molecular sieve is a plate-like laminate having a thickness of more than 50 nm. The silica to alumina ratio of the product was 69.6.
Comparative example 2
The procedure of example 1 was repeated, except that no urea was added.
The SEM photograph of the prepared ZSM-22 molecular sieve is shown in figure 4, and the crystal of the molecular sieve is in an oval plate shape and has the thickness of more than 50 nanometers. The silica to alumina ratio of the product was 162.
Comparative example 3
The procedure of example 1 was followed, except that the templating agent was hexamethylenediamine.
The solid product obtained is a rod-shaped ZSM-22. The silica to alumina ratio of the product was 154.
Comparative example 4
Except that the material ratio (mol ratio) of the reactants is as follows: SiO 22/Al2O3600; 1-Ethyl pyridine bromide/SiO2＝0.3；OH-/SiO2＝0.2；H2O/SiO218; urea-/SiO2The procedure of example 1 was repeated except that 0.1 was used.
The solid product obtained was ZSM-22 with crystals in the form of oval platelets, with partial stacking between the platelets, and an average thickness of 50 nm. The silicon to aluminum ratio of the product was 394.
Comparative example 5
Except that the material ratio (mol ratio) of the reactants is as follows: SiO 22/Al2O3180; 1-Ethyl pyridine bromide/SiO2＝0.65；OH-/SiO2＝0.2；H2O/SiO218; Urea/SiO20.1 outerOtherwise, the same procedure as in example 1 was repeated.
The solid product obtained is ZSM-22 in the form of oval platelets, with partial stacking between the platelets, having an average thickness of greater than 50 nm. The silicon to aluminum ratio of the product was 172.
Comparative example 6
Except that the material ratio (mol ratio) of the reactants is as follows: SiO 22/Al2O3180; 1-Ethyl pyridine bromide/SiO2＝0.3；OH-/SiO2＝0.75；H2O/SiO218; Urea/SiO2The procedure of example 1 was repeated except that 0.1 was used.
The solid product obtained is a needle-shaped ZSM-22 molecular sieve with an average particle size of 10 x 100 nm. The silica to alumina ratio of the product was 109.
Comparative example 7
Except that the material ratio (mol ratio) of the reactants is as follows: SiO 22/Al2O3180; 1-Ethyl pyridine bromide/SiO2＝0.3；OH-/SiO2＝0.2；H2O/SiO218; Urea/SiO2The procedure of example 1 was repeated except that 0.70 was used.
The solid product obtained is ZSM-22 in the shape of oval plate, and partial stacks exist among the plate crystals, and the average thickness of the plate crystals is more than 50 nanometers. The silica to alumina ratio of the product was 165.
It should be noted that the above-mentioned embodiments are only for explaining the present invention, and do not constitute any limitation to the present invention. The present invention has been described with reference to exemplary embodiments, but the words which have been used herein are words of description and illustration, rather than words of limitation. The invention can be modified, as prescribed, within the scope of the claims and without departing from the scope and spirit of the invention. Although the invention has been described herein with reference to particular means, materials and embodiments, the invention is not intended to be limited to the particulars disclosed herein, but rather extends to all other methods and applications having the same functionality.
Claims (9)
1. A method for preparing a ZSM-22 molecular sieve comprises the steps of carrying out crystallization treatment on a mixture formed by a silicon source, an aluminum source, an alkali source, a template agent, urea and water to obtain the molecular sieve;
in the mixture, SiO is used2Calculated silicon source, calculated as Al2O3Calculated as Al source and OH-The calculated molar composition of the alkali source, the urea, the template and the water is as follows: SiO 22/Al2O315 to 500; templating agent/SiO20.01 to 0.5; OH group-/SiO20.01 to 0.50; h2O/SiO29 to 30; Urea/SiO20.005 to 0.50;
the template agent is 1-ethyl pyridine bromide.
2. The method of claim 1, wherein the mixture is SiO2Calculated silicon source, calculated as Al2O3Calculated as Al source and OH-The calculated molar composition of the alkali source, the urea, the template and the water is as follows: SiO 22/Al2O320 to 400; templating agent/SiO20.05 to 0.5; OH group-/SiO20.05 to 0.40; h2O/SiO210 to 26; Urea/SiO20.01 to 0.40.
3. The method of claim 1 or 2, wherein the silicon source comprises at least one of silica gel, silica sol, and tetraalkyl silicate.
4. The method of claim 3, wherein the silicon source is silica sol.
5. The method of claim 1 or 2, wherein the aluminum source comprises at least one of sodium aluminate, aluminum nitrate, aluminum sulfate, aluminum oxide, aluminum hydroxide, and aluminum isopropoxide.
6. The process of claim 5 wherein the aluminum source is sodium aluminate.
7. The method according to claim 1 or 2, wherein the crystallization conditions comprise: the crystallization temperature is 80-180 ℃; the crystallization time is 10 hours to 10 days.
8. The method of claim 7, wherein the crystallization conditions comprise: the crystallization temperature is 100-180 ℃; the crystallization time is 1-5 days.
9. The ZSM-22 molecular sieve prepared according to any of claims 1-8, the molecular sieve crystals having a platelet morphology with a crystal thickness of 8-20 nm.
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| CN104528757A (en) * | 2014-12-16 | 2015-04-22 | 上海华谊（集团）公司 | Preparation method of nanoscale MCM-22 molecular sieve |
| CN107285332A (en) * | 2016-04-12 | 2017-10-24 | 中国石油化工股份有限公司 | The synthetic method of ZSM-22 molecular sieves and its ZSM-22 molecular sieves of synthesis |
| CN109502607A (en) * | 2018-11-30 | 2019-03-22 | 中国科学院山西煤炭化学研究所 | A kind of synthetic method of nanometer of ZSM-22 molecular sieve |
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| CN104528757A (en) * | 2014-12-16 | 2015-04-22 | 上海华谊（集团）公司 | Preparation method of nanoscale MCM-22 molecular sieve |
| CN107285332A (en) * | 2016-04-12 | 2017-10-24 | 中国石油化工股份有限公司 | The synthetic method of ZSM-22 molecular sieves and its ZSM-22 molecular sieves of synthesis |
| CN109502607A (en) * | 2018-11-30 | 2019-03-22 | 中国科学院山西煤炭化学研究所 | A kind of synthetic method of nanometer of ZSM-22 molecular sieve |
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| Title |
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| Synthesis and crystal growth mechanism of ZSM-22 zeolite nanosheets;Yi Luo等;《CrystEngComm》;20160620;第18卷;第5611-5615页 * |
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